Manufacturing of carbon monoxid and hydrogen.



R. P. PICTET.

MANUFACTURING OF CARBON MONOXID AND HYDROGEN.

APPLICATION FILED JULY I, 1912;

132%8 l 8, Patented June 5, 1 917.

Oxygen RAOUL PIERRE PIO'I'E'IQOF WILMERSJDORF, NEAR BERLIN, GERMANY.

MANUFACTURING CARBON IVIONOXID AND HYDROGEN.

Original application iiled May 29, 1911, Serial No. 630,177. Divided.and

- Serial No. 707,034.

To all whom it may concern.-

Be it known that I, RAoUL PIERRE Pio'rn'r, a citizen of the SwissRepublic, residing at 116 Uhlandstrasse, Wilmersdorf, near Berlin,Germany, have invented certain new and useful Improvements in theManufacturing of Carbon Monoxid and Hydrogen;

and I do hereby declare the following to be a full, clear, and exactdescription of the invention, such as will enable others skilled in theart to which it appertains to make and use the same.

In my application for patent filed May 29, 1911, Serial No. 630,177, andof which this application is a division, I have described themanufacture of hydrogen from hydrocarbons, such as petroleum, crude oil,lubricatin oils, solar oils, parafiin oils or gasolene, etc., by passingtheir vapors through a highly heated tube.

For many industrial purposes pure hydrogen is either not necessary ornot desirable, and a mixture of hydrogen and carbon monoxid is preferredto pure hydrogen.

In the application above referred to I increase the yield of availablegas produced, at the same time increasing the quantity of hydrogenproduced with the use of the starting materials described, by using inconjunction with such starting materials oxids of hydrogen, H 0, 11,0the latter being water and oxygen.

Oxygen combines with carbon at high temperatures to form carbon-monoxid,and instead of using oxygen alone, or air, it is advantageous to useoxids or their equivalents, which under the action of heat will increasethe quantity of hydrogen in the resulting gas.

The substances are decomposed by the high heat, the oxygen uniting withthe car: bon of the hydrocarbon vapor used, to form carbon-monoxid, andthe hydrogen remaining unchanged and increasing the volume of hydrogenobtainable from the hydrocarbon alone.

The hydrocarbon or oils may be vaporized separately from the water, orit may be mixed with the water, and if desired, the re-. quiredquantityof oxygen may be supplied to the mixture, when H O, is desired to beused with the hydrocarbon.

' I also proceed by introducing the hydrocarbon vapor at one end of thepi e separately from the water vapor (steamg which Specification ofLetters Patent.

Patented June 5, 1917.

this application filed July 1, 1912.

may or may not be mixed with oxygen.

Good results are obtained by separately supplylng the hydrocarbon vapor,steam and oxygen to the inlet end of the heated decomposing pipe, therelative proportions of which, however, should be regulated so that theresultin gas will be a mixture of hydrogen and car on monoxid. I

The pipe, preferably of iron in the commercial process, is heated tonear its melting point. i

If petroleum be the type of hydrocarbon used, 1 kg. of'petroleum-Willproduce about 700 g. of soot (carbon), about 200 g. of pure hydrogen,and about 100 g. of heavy vapors of hydrocarbon which are not decomposedat the temperature of about the melting point of carbon.

7 00 g. of carbon require when heated with oxygen, as 1s well known, 933g. of oxygen to convert it into carbon monoxid. NOW when 1050 g. ofwater is decomposed, there is produced 933 g. of oxygen and 117 g. ofhydrogen. Each gram molecule of water requires 68.36 calories of heat toefiect its decomposition, and each gram molecule of carbon monoxidproduces, during its formation 29 calories.

' In using 1kg. of-petroleum for producing hydrogen and carbon monoxidwith the aid of 1050 g. of water, so as to cause the 7 00 g. of carbonto combine with 938 of oxygen to form 1603 g. carbon monoxld, 2294:calories Will have to be supplied through the walls of the iron pipe inwhich the reaction is performed.

This quantity. of heat, namely 2294 calories, must be supplied throughthe walls of the tube or pipe in addition to the heat required forconverting the petroleum vapor into carbon and methane and the methaneinto carbon and hydrogen.

The pipe that is employed, for example, iron pipe, must of course belengthened in proportion to the quantity of heat to be supplied. If itwere wished to supplythe heat, 2204 calories, through the walls of ashort pipe by increasing the temperature by a more intense furnace, itcould not be done to the use of a quantity of water less than.

taneously allowed to flow into a boiler. These two substances are thenvaporized and their mixed vapors are caused to flow through an iron pipeheated almost to its melting point. The following maximum quantities ofsubstances will be obtained:

By the d composition of the methane from the petroleum, 2220 l. ofhydrogen; by the decomposition of the steam. 1300 l. of hydrogen; by thecombustion of 700 g. of carbon, 1633 or 1307 l. of carbon monoxid, therebeing a residue of 100 g. of undecomposed coal tar oils. The totalvolume of the gas mixture finally obtained from 1 kg. of petroleum is4827 l. composed of 3520 l. of hydrogen and 1307 carbon monoxidcalculated at 0 C. and 760 mm.

The buoyancy of the gas mixture is 0.887 per liter, and the specificweight 0.406.

The heat of combustionof the gas mixture is 3022 calories per cu. m.

This mixture ofgases is advantageously used for autogenous welding,because the carbon monoxid has a high reducing action.

An important advantage of my process consists in the possibility, byregulating the supply of water, of forming any desired quantity ofcarbon monoxid from the carbon in the petroleum, the remaininguncombined carbon settling in the condenser into which the pipedischarges.

When using peroxid of hydrogen or, preferably, its equivalent, watervapor and oxygen, the quantity of uncombined carbon due that sufiicentto convert all the carbon into carbon monoxid or otherwise, will bereduced. r

It has also been found that complete conversion of carbon to carbonmonoxid does not take place because, on the one hand the temperature ofdecomposition of the steam in the presence of finely divided carbon, ishigher than that of the hydrocarbons, and,

on the other hand, a deficit of 30 calories is obtained owing to theheat absorbed by each gram molecule of water entering the pipe in theform of steam.

By the use of the higher oxid of hydrogen,

that is, by the use of oxygen in addition to steam, the temperature ofthe. pipe need not be kept too close to its melting point, and thereby asafer commercial operation is provided, by lessening the danger ofburning out the apparatus.

It has been observed that at about 1300 (l, 2025% of'the water suppliedis converted into gas. If the temperature approaches 14001500 0., theproportion is' increased two-fold or three-fold, 2'. 6., almost completeconversion of the water into gas takes place.

The hydrocarbon vapor and the steam mixed with oxygen are supplied tothe hot vaporous hydrocarbon molecules, that have already been or arebeing decomposed to form carbon in stem nascendi. This very hot carbonis capable of decomposing the water and at the same time forms carbonmonoxid. As the carbon in the initial portion of the tube is in excess,each gram molecule of carbon monoxid formed from the oxygen and theoxygen of the decomposed water supplies 29 calories.

When a suitable quantity of oxygen is supplied, all the carbon can beconverted into carbon monoxid without having to increase the internaltemperature of the pipe. The heat consumed by the decomposition of thewater is supplied by the heat of formation of the carbon monoxid. Inpractice, therefore, the Pipe need only be heated to the temperaturesuflicient for the decomposition of the hydrocarbon, about 1350 C.

The fire surrounding the pipe has merely to supply the heat necessary toraising the vapors entering the pipe to the decomposition gtemperatureof the hydrocarbon. As

all the chemical reactions taking place in the pipe mutually bring aboutthermal equilibrium, the external temperature of the pipe will beconsiderably lower than when no oxygen is supplied to it, and the dangerof melting the pipe is decreased, and it may also be made shorter.

The resulting gas mixture is composed of hydrogen and carbon monoxidwith but small quantities of nitrogen and carbon dioxid. I believe I amthe first to produce such a mixture by a continuous process.

Oxygen made from any source maybe used, but that obtained by thedistillation of liquid air has been found particularly suitable for thepurpose.

In the drawing, which is a diagrammatic view of an apparatus, A is theboiler in which the oil or oil and water is placed to supply the oilvapor or mixed oil vapor and steam through a pipe B provided with avalve C to the decomposing pipe D. This pipe D is placed in a suitablefurnace chamber E provided with an exit F for products of combustion.The pipe D is heated by burners G supplied with combustion gas by a pipeH.

A separate steam supply pipe I and oxygen supply pipe K are provided, asshown, to simultaneously or independently supply steam and oxygen.

The decomposition pipe D is connected to and discharges into a coil Lhaving a sludge spray N and discharges at 0 into a suitable storagevessel.

I claim 1. A process for manufacturing a hydrogen-carbon monoxid mixturefrom hydro carbonaceous material, whichv comprises simultaneouslyadmitting said material, steam and oxygen to a conduit heatedsuficiently to decompose the steam and hydrocarbon.

2. A process for the manufacture of a hydro en-carbon monoxid mixturefrom hydrocar onaceous material, which comprises simultaneouslyadmitting said material,

steam, and oxygen to a conduit heated suficiently to decompose the steamand hydrocarbon and initiate the reaction, the oxygen being suflicientto produce the heat of oxidation of the carbon required to establish theequilibrium of the reaction.

In testimony that Iclaim the foregoing as 2 my lnvention I have signedmy name in presence of two subscribing witnesses.

RAOUL PIERRE PICTET. Witnesses: AUGUST 0. P101121 I HERBERT D. JAMnsoN.

